Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
  • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
  • C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
  • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
  • A01N39/04—Aryloxy-acetic acids; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
  • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/20—N-Aryl derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
  • C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
  • C07C229/30—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and unsaturated

Definitions

• the present invention relates to derivatives of 3-aminobutenoic acid, also known as 3-aminocrotonic acid.
• aminobutenoic acid derivatives are known and most often find use in the preparation of a wide range of chemical compounds, often heterocyclic compounds which are themselves intermediates for or compounds having biological activity.
• European Patent Specification No. 245130A discloses herbicidally active pyridinecarboxylic acid derivatives and, as intermediates, various 3-amino-4,4,4-trifluorobutenoates. No biological activity of any kind is suggested for those intermediates.
• German Offenlegungsschrift No. 23 36 723 discloses a large group of compounds as having herbicidal activity, which group includes alkylated-­amino-propenoate and -butenoate derivatives with mono- or di-substitution of the amino group, though specific exemplification of herbicidal properties is only provided for the propenoate derivatives.
• the present invention provides a compound of the general formula in which R1 represents an optionally substituted alkyl, alkenyl, alkynyl, aryl or aralkyl radical; R2 represents a chlorine atom, a group of the general formula O - - R5, wherein R5 represents a hydrogen atom or an optionally substituted alkyl, alkoxy, alkoxycarbonyl, aryl, aralkyl, aryloxy, aralkoxy, aryloxyalkyl or amino radical, or a group of the general formula O-R6 wherein R6 represents an optionally substituted heterocyclic ring of which at least the ring member bonded to the oxygen atom or one of the two adjacent ring members is a hetero atom; and one of R3 and R4, represents a hydrogen atom and the other represents an alkyl radical.
• alkyl, alkenyl or alkynyl radical, or an alkyl moiety in an alkoxy or aralkyl radical may be a straight or branched chain radical.
• an alkyl radical or moiety has from 1 to 12 carbon atoms, preferably from 1 to 6, especially from 1 to 4, carbon atoms.
• Alkenyl and alkynyl radicals suitably have from 2 to 12 carbon atoms, preferably from 2 to 6, especially from 2 to 4, carbon atoms.
• An aryl radical, or an aryl moiety in an aralkyl or aryloxy radical may be a single or fused carbocyclic ring system having from 6 to 10 ring members.
• an aryl radical or moiety comprises a single ring system and preferably is a phenyl ring.
• a heterocyclic radical is suitably a single or fused, saturated or unsaturated ring system having from 5 to 10 ring members of which from 1 to 3 ring members may be hetero atoms selected from oxygen, nitrogen and sulphur atoms, with either at least one hetero atom being adjacent, or alpha to, the ether-carbon ring member or the ring member bonded to the ether-oxygen atom being a suitable hetero atom, for example a nitrogen atom.
• Radicals represented by the symbols R1, R5 and R6 may be unsubstituted or substituted.
• the substituent groups may be any of those customarily employed in the modification and/or development of pesticidal compounds and are especially substituents that maintain or enhance the herbicidal activity associated with the butenoate compounds of the present invention, or influence persistence of action, soil or plant penetration, or any other desirable property of such herbicidal compounds. There may be one or more of the same or different substituents present in each radical.
• substituent groups include halogen atoms, especially fluorine, chlorine or bromine atoms, nitro groups, cyano groups, free or modified hydroxy groups, free or modified carboxy groups, alkyl groups unsubstituted or substituted by one or more halogen atoms, especially fluorine atoms, and aryl groups unsubstituted or substituted by one or more halogen atoms, especially chlorine atoms, or nitro, cyano or haloalkyl groups.
• Modified hydroxy and carboxy groups are to be understood to be groups derived from hydroxy or carboxy groups by, for example, etherification, esterification, acylation or salt formation, as appropriate for the group in question.
• An alkyl radical when present as a substituent, preferably has from 1 to 4 carbon atoms, especially 1 or 2 carbon atoms, and as a halogen-substituted alkyl group, a trifluoromethyl group may especially be mentioned.
• An aryl radical when present as a substituent, is preferably a phenyl group, and as a halogen-substituted aryl group, a 4-chlorophenyl group may especially be mentioned.
• radical R1 examples include optionally substituted C1 ⁇ 6 alkyl, C2 ⁇ 6 alkenyl, C2 ⁇ 6 alkynyl, phenyl and aryl(C1 ⁇ 6)alkyl groups.
• the group R1 is selected from C1 ⁇ 4 alkyl, C2 ⁇ 4 alkenyl, phenyl and phen(C1 ⁇ 4)alkyl groups.
• the group R1 is a methyl, ethyl, propyl, butyl, allyl or benzyl group, and R1 is especially an unsubstituted methyl, ethyl, tert butyl, allyl or benzyl group.
• one of the radicals R3 and R4 represents a hydrogen atom and the other represents a C1 ⁇ 6 alkyl radical.
• one of the radicals R3 and R4 represents a hydrogen atom and the other represents a C1 ⁇ 4 alkyl, especially a methyl group.
• the radical R2 may represent a chlorine atom, a group O - - R5 or a group O-R6.
• Suitable examples of the group O - - R5 include optionally substituted formyl, (C1 ⁇ 6)alkyl carbonyl, (C1 ⁇ 6)alkoxycarbonyl, (C1 ⁇ 6)alkoxycarbonyl­carbonyl, arylcarbonyl, or aryl (C1 ⁇ 6)alkylcarbonyl, aryloxycarbonyl, aryloxy(C1 ⁇ 6)alkylcarbonyl, carbamoyl and arylcarbamoyl groups.
• radical R6 examples include optionally substituted tetrahydrofuran-2-yl, tetrahydropyran-2-yl, pyrid-1 or 2-yl, isobenzylfuran- 1-yl, chroman-2-yl, chromen-2-yl, isoxazol-2 or 3-yl, furazan-2 or 3-yl and morpholin-2, 3- or 4-yl.
• the radical R2 represents a chlorine atom; a group O - - R5 in which R5 represents a hydrogen atom, a C1 ⁇ 4 alkyl, for example methyl, ethyl or propyl, group, a C1 ⁇ 4 alkoxy group, for example a methoxy group, a C1 ⁇ 4 alkoxycarbonyl group, for example a methoxycarbonyl group, an aryl group, for example a phenyl group, an aryl (C1 ⁇ 4)alkyl group, for example a benzyl group, an aryloxy group, for example a phenoxy group, an aryl (C1 ⁇ 4)alkoxy group, for example a benzyloxy group, or an aryloxy(C1 ⁇ 4)alkyl group, for example a phenoxymethyl group, each of which being optionally substituted, or an amino group, preferably mono- or di-substituted, for example a phenylamino group; or
• the compounds of the present invention have an assymetric carbon atom and therefore that compounds of the general formula I may exist in different stereoisomeric forms. Furthermore, the compounds of the general formula I may exist in both E and Z stereoisomeric form. Therefore the compounds of the recent invention may exist in four stereoisomeric forms.
• the present invention encompasses all stereoisomers of the compounds of general formula I whether free from other isomers or admixed with other isomers in any proportion, and thus includes, for example, racemic mixtures of enantiomers.
• the present invention further provides a process for the preparation of a compound of the general formula I which comprises either a) reacting at reduced temperature, a compound of the general formula in which R1 is as hereinbefore defined, with a compound of the general formula in which R2, R3 and R4 are as hereinbefore defined, and X represents a leaving group, or b) reducing a compound of the general formula in which R1, R2, R3 and R4 are as hereinbefore defined.
• a leaving group represented by X is any group that will, under the reaction conditions, cleave from the starting material thus promoting reaction at a specified site.
• the group X in a compound of general formula III may be, for example, a halogen atom, preferably a chlorine or bromine atom, but is especially a chlorine atom.
• the reaction a) is suitably carried out under basic conditions, for example in the presence of an alkali metal or alkaline earth metal hydroxide or bicarbonate, or a tertiary amine, suitably triethylamine or pyridine. Also the reaction a) is suitably carried out in a solvent inert to the reaction media, which solvent is conveniently an organic solvent, for example diethyl ether or a chlorinated hydrocarbon, e.g. dichloromethane.
• solvent is conveniently an organic solvent, for example diethyl ether or a chlorinated hydrocarbon, e.g. dichloromethane.
• reaction of compounds II and III is carried out at a temperature below 0°C, preferably at a temperature in the range of from -50 to -80°C, especially between -70 and -80°C, and allowed to warm, while the reaction is occurring, to ambient temperature.
• substantially equimolar amounts of reactants II and III may be utilised.
• the reaction b) is suitably carried out under reducing conditions usual in the art for such reactions.
• the reduction is effected by conventional hydrogenation techniques, especially by catalytic hydrogenation using hydrogen gas, or a compound or mixture of compounds that generate hydrogen in situ , in conjunction with a platinum or palladium on carbon catalyst.
• a platinum oxide catalyst should be employed in preference to a palladium/carbon catalyst.
• the resulting compound of the present invention may, if desired, be isolated and purified using conventional techniques, for example solvent extraction, evaporation and then recrystallisation or chromatography on silica.
• R2 is other than a chlorine atom
• R1, R3 and R4 are as hereinbefore defined, by conventional esterification or acylation procedures, for example by reaction with a compound of the general formula R5COHal, in which R5 is as hereinbefore defined, but preferably is other than an amino group, and Hal represents a halogen atom, in a suitable base, for example triethylamine, or by reaction with an isocyanate of the general formula R7CO, in which R7 represents an optionally substituted imino group, suitably at reduced temperature.
• the present invention further provides the use of a compound of the present invention as a herbicide.
• the present invention additionally provides a herbicidal composition which comprises a compound of the invention in association with a carrier. More than one carrier may be present in a composition of the invention and suitably at least one carrier is a surface-active agent.
• the present invention provides a method of combating undesired plant growth at a locus by treating the locus with a compound or composition of the invention.
• Application to the locus may be pre-emergence or post-emergence.
• the dosage of active ingredient applied is suitably in the range of from 0.01 to 10 kg/ha, preferably from 0.05 to 5 kg/ha.
• a carrier in a composition according to the invention is any material with which the active ingredient is formulated to facilitate application to the locus to be treated, which may for example be a plant, seed or soil, or to facilitate storage, transport or handling.
• a carrier may be a solid or a liquid, including a material which is normally gaseous but which has been compressed to form a liquid, and any of the carriers normally used in formulating herbicidal compositions may be used.
• compositions according to the invention contain 0.5 to 95% by weight of active ingredient.
• Suitable solid carriers include natural and synthetic clays and silicates, for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium silicates, for example kaolinites, montmorillonites and micas; calcium carbonate; calcium sulphate; ammonium sulphate; synthetic hydrated silicon oxides and synthetic calcium or aluminium silicates; elements, for example carbon and sulphur; natural and synthetic resins, for example coumarone resins, polyvinyl chloride, and styrene polymers and copolymers; solid polychlorophenols; bitumen; waxes; and solid fertilisers, for example superphosphates.
• natural and synthetic clays and silicates for example natural silicas such as diatomaceous earths; magnesium silicates, for example talcs; magnesium aluminium silicates, for example attapulgites and vermiculites; aluminium
• Suitable liquid carriers include water; alcohols, for example isopropanol and glycols; ketones, for example acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic or araliphatic hydrocarbons, for example benzene, toluene and xylene; petroleum fractions, for example kerosine and light mineral oils; chlorinated hydrocarbons, for example carbon tetrachloride, perchloroethylene and trichloroethane. Mixtures of different liquids are often suitable.
• compositions are often formulated and transported in a concentrated form which is subsequently diluted by the user before application.
• a carrier which is a surface-active agent facilitates this process of dilution.
• at least one carrier in a composition according to the invention is a surface-active agent.
• the composition may contain at least two carriers, at least one of which is a surface-active agent.
• a surface-active agent may be an emulsifying agent, a dispersing agent or a wetting agent; it may be nonionic or ionic.
• suitable surface-active agents include the sodium or calcium salts of polyacrylic acids and lignin sulphonic acids; the condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in the molecule with ethylene oxide and/or propylene oxide; fatty acid esters of glycerol, sorbitol, sucrose or pentaerythritol; condensates of these with ethylene oxide and/or propylene oxide; condensation products of fatty alcohol or alkyl phenols, for example p -octylphenol or p -octylcresol, with ethylene oxide and/or propylene oxide; sulphates or sulphonates of these condensation products; alkali or alkaline earth metal salts, preferably sodium salts, of sulphuric or
• compositions of the invention may for example be formulated as wettable powders, dusts, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.
• Wettable powders usually contain 25, 50 or 75% w of active ingredient and usually contain in addition to solid inert carrier, 3-10% w of a dispersing agent and, where necessary, 0-10% w of stabiliser(s) and/or other additives such as penetrants or stickers.
• Dusts are usually formulated as a dust concentrate having a similar composition to that of a wettable powder but without a dispersant, and are diluted in the field with further solid carrier to give a composition usually containing 1 ⁇ 2-10% w of active ingredient.
• Granules are usually prepared to have a size between 10 and 100 BS mesh (1.676 - 0.152 mm), and may be manufactured by agglomeration or impregnation techniques. Generally, granules will contain 1 ⁇ 2-75% w active ingredient and 0-10% w of additives such as stabilisers, surfactants, slow release modifiers and binding agents. The so-called “dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient.
• Emulsifiable concentrates usually contain, in addition to a solvent and, when necessary, co-solvent, 10-50% w/v active ingredient, 2-20% w/v emulsifiers and 0-20% w/v of other additives such as stabilisers, penetrants and corrosion inhibitors.
• Suspension concentrates are usually compounded so as to obtain a stable, non-sedimenting flowable product and usually contain 10-75% w active ingredient, 0.5-15% w of dispersing agents, 0.1-10% w of suspending agents such as protective colloids and thixotropic agents, 0-10% w of other additives such as defoamers, corrosion inhibitors, stabilisers, penetrants and stickers, and water or an organic liquid in which the active ingredient is substantially insoluble; certain organic solids or inorganic salts may be present dissolved in the formulation to assist in preventing sedimentation or as anti-freeze agents for water.
• Aqueous dispersions and emulsions for example compositions obtained by diluting a wettable powder or a concentrate according to the invention with water, also lie within the scope of the invention.
• the said emulsions may be of the water-in-oil or of the oil-in-water type, and may have a thick 'mayonnaise'-like consistency.
• composition of the invention may also contain other ingredients, for example other compounds possessing herbicidal, insecticidal or fungicidal properties.
• the tests fall into two categories, pre-emergence and post-emergence.
• the pre-emergence tests involved spraying a liquid formulation of the compound onto the soil in which the seeds of the plant specied mentioned above had recently been sown.
• the post-emergence tests involved two types of test, viz., soil drench and foliar spray tests. In the soil drench tests the soil in which the seedling plants of the above species were growing was drenched with a liquid formulation containing a compound of the invention, and in the foliar spray tests the seedling plants were sprayed with such a formulation.
• the soil used in the tests was a prepared horticultural loam.
• the formulations used in the tests were prepared from solutions of the test compounds in acetone containing 0.4% by weight of an alkylphenol/ethylene oxide condensate available under the trade mark TRITON X-155. These acetone solutions were diluted with water and the resulting formulations applied at dosage levels corresponding to 5 kg or 1 kg of active material per hectare in a volume equivalent to 600 litres per hectare in the soil spray and foliar spray test, and at a dosage of level equivalent to 10 kilograms of active material per hectare in a volume equivalent to approximately 3,000 litres per hectare in the soil drench tests.
• the herbicidal effects of the test compounds were assessed visually twelve days after spraying the foliage and the soil, and thirteen days after drenching the soil and were recorded on a 0-9 scale.
• a rating 0 indicates growth as untreated control, a rating 9 indicates death.
• An increase of 1 unit on the linear scale approximates to a 10% increase in the level of effect.

Landscapes

• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Environmental Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Plant Pathology (AREA)
• Pest Control & Pesticides (AREA)
• Agronomy & Crop Science (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Plural Heterocyclic Compounds (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=10655933

Family Applications (1)

Country Status (7)

Cited By (1)

Citations (2)

• 1989
  • 1989-04-28 GB GB898909809A patent/GB8909809D0/en active Pending
• 1990
  • 1990-04-25 KR KR1019900005830A patent/KR900016112A/ko not_active Application Discontinuation
  • 1990-04-26 EP EP90201067A patent/EP0395182A1/de not_active Withdrawn
  • 1990-04-26 AU AU53960/90A patent/AU5396090A/en not_active Abandoned
  • 1990-04-26 BR BR909001940A patent/BR9001940A/pt unknown
  • 1990-04-26 CA CA002015500A patent/CA2015500A1/en not_active Abandoned
  • 1990-04-26 JP JP2108993A patent/JPH03204845A/ja active Pending

Patent Citations (2)

Non-Patent Citations (6)

Also Published As

Similar Documents

Legal Events